The bimetallic Au-Cu alloy nanoparticles have been constructed in electrospun carbon nanofibers (Au-Cu/CNFs), employing as high efficient hydrogen evolution reaction (HER) electrode. The morphology, structure, and composition of bimetallic Au-Cu alloy can be controlled by adjusting the precursor nanofibers through a facile approach. With the increased Cu content, the Au-Cu alloy have a transition from the homogeneous AuCu3 alloy phase to the Au(3)Cn phase with Cu shell. The self-supported bimetallic Au-Cu/CNFs hybrid can be directly employed as electrode materials for water splitting, and it showed excellent electrochemical activity, including long-term stability, high exchange current density, and low overpotential. The outstanding HER performance could be mainly attributed to the synergistic interactions and interfacial effects of Au-Cu alloy with high densities of uncoordinated surface atoms. In addition, the fast charge transport and the fast kinetic for the desorption of the gas were originated from the self supported three-dimensional architectures consist of integrated Au-Cu/CNFs networks. The Au-Cu/CNFs with mass ratio of 1:2 (Au3Cu-Cu "core-shell" alloy) obtain the lowest overpotential of 83 mV (at j = 10 mA cm(-2)), lowest Tafel slope of 70 mV dec(-1), and highest exchange current density of 0.790 mA cm(-2). The present investigations offer a new strategy for the design and synthesis of unique nanocrystals in energy conversion related application.